Steroidal compounds and methods for obtaining the same



UNITED STATES 3 PATENT OFFICE 7 STEROIDAL COMPOUNDS AND METHODS FOR OBTAINING THE SAME Romeo B. Wagner, State College, Pa., assignor to Parke, Davis & Company, Detroit, Mich., a corporation of Michigan No Drawing. Application May 15, 1944, Serial No. 535,755

8 Claims. (Cl. 260239.5)

ee aso J m hem. Soc 65, 1199 (1943)) acetate However, pseudo-agavogemn forms a ese compounds are valuable as intermediates tetraaceta 42, since its group at C-12is for the preparation of hormones of the sex 011 hormone type and particularly of the adrenal cortex hormone type since they are oxygenated at position of the ster d nucleus 10 The invention may be illustrated by the following examples. scribed in detail in the copending Patents Nos. Pseudomanogenin 2,352,848 and 2,352,852, issued July 4, 1944. These also include proof of structure of the 15 1 Amlxture 9f 10 of-manogenm dH-a'cetate and pseudo-genin side chain.

is invention relates to the preparation of pseudo-genius having the formula,

CH3 CH3 /OH2OH2 needles of M. P. 168-171" 0.; yield is 6 grams of O=0 0343B; 0 pseudomanogenin triacetate. I I CH=Y Anal.: Calcd. for 0231-14803! C, 69.2; H, 8.5%.

H Found: C, 69.4; H, 8.3%. Alkaline hydrolysis gives free pseudomanogenin Y"=/\ H from the triacetate. l Pseudomemogem'n A solution of 5 g. of mexogenin in 15 cc. of where Y and Y" e i h case members f acetic anhydride is heated at 200 C. for 12 hours the class in a sealed tube. The solvent is removed and the 0H residue is hydrolyzed with 200 cc. of boiling 5% alcoholic potassium hydroxide for 30 minutes. H The hydrolysis mixture is extracted with ether and the ethereal solution is washed and evapo d ps hydrolyzable to rated until crystals start to appear and is then 6 cooled. The crystals are then separated and recrystallized from acetone, M. P. 143l45 C.

H Yield is 3 grams of pseudomexogenin. Anal: Calcd. for C27H4205. C, 72.6, H, 9.5%. and Y 1s a member of the class =0, Found; c 72 H, 9 4

OH By starting with mexogenin diacetate or like lower fatty acid d acylate and treatin as de- H scribed above for manogenin diacetate, onecan 7 obta n pseudomexogenin triacylate or triacetate and groups hydmh Zable to Agavogenin can e similarly treated either to OH obtain pseudoagavogenin or its tetraacylate.

W ile for ease of manipulation and economy H the preferred isomerizing agent is acetic anhy- Specifi examples f this type Com ound are dride, other lower aliphatic acid anhydrides may p-seud man i in which y two I also be used. The preferred temperature range groups are each 00 hes between 190 and 200 C. although the re- OH action also takes place as low as or as high as 230". The example is intended as illustrative H at C-27, 0-2 and C-3 of the nucleus, respectively, 5 In addition to using ethanolic KOH solution for 4 hydrolyzing the acylated pseudogenin to the free and groups hydrolyzable to genin, one can use any other suitable alkaline so- OH lution, for example one containing NaOH, K2003,

KHCOz, NazCOa, NaHCOs or the like. If an alco- H hol is required to aid hydrolysis, this can be 5 methanol Or other lower aliphatic alcohol instead 2. Compounds of the formula, of ethanol.

. Y 011 CH CH The formulas for pseudomanogenm, pseudomexogenin and pseudoagavogenin described above are: v 011:! on O OH CH3 1 a E==c omom Y v (DH-CH; H I Y:

HO H

where Y and Y" are in each case members oi the H0 1 Class 1 OH H Pseudmmanogenin I H fi dlw b ll id t hd a a an 0 er car oxy 0 ac es er groups y rolyzable to (Ell-CH: OH

and Y is a member of the class =0,

"V OH Pscudo-mexogenin H HO OH CH5 CH3 a and lower carboxylic acid ester groups hydrolyzable to V GEL-CH3 OH omon 0 H E0 3. A pseudo-manogenin compound of the formula,

H 0 CH3 Pseudo-agavogenln- CH/\CH3 (E:C CE1CH2 The acylates ofthese, such as the acetates, have oH-om the same formulas except that the OH groups'are N 2 replaced by acyl or acetyl (CHSCOO). fi What I claim is: r Y H 1. Compoundsoi the formula, H

Y Y! om omom t CH3 (2 0 OH on H (\JHZY V where Y and Y are members of the class OH Oacyl v -O Y 11 and 11 4. A pseudo-mexogenin compound having the formula, where Y and Y" are in each case members of the 00 CH 0 CH CH: class OH )K (E o-omen, (EH-CH;

H omY and groups hydrolyzable to 7 OH H imay, is amemberoftheclass=o where Y and, Y" are members of the class OH OH O -acyl and 2,408,831 5. A pseudo-agavogenin compound having the 7. Pseudo-mexogenln having the formula, fcrmula,

CH CH Y' OH CH: CH: CH3 6 a C CH CH 3 I 3 =C-CH3(|3H2 x Q 2 H (BEECH: CH-CH;

OHY 0112011 l/ f\ H f H 10 H0 K Y I I B 1 Where Y, Y and Y are members of the class Pseudo agavogenm having the formu OH Oacyl CH; 011, E and A =O CH('3H H I OH-OH: 6Q Pseudo-manogenin having the formula, HBOH HO \/\H O CH: 0H; CH3 (j:

)k =O-CHzC-H2 HO 0H-0H8 1'1 HO I V; CHaOH I 7 HOW ROMEO B. WAGNER. 

